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| United States Patent |
5,015,767
|
|
Maignan
, et al.
|
May 14, 1991
|
N-(mercaptoalkyl).OMEGA.-hydroxyalkylamides and their use as a reducing
agent in a process for permanently deforming hair
Abstract
An N-(mercaptoalkyl).OMEGA.-hydroxyalkylamide having the formula,
##STR1##
wherein n is 2 or 3 and m is 2 to 5 inclusive is employed as a reducing
agent in the first stage reducing operation of permanently deforming hair.
| Inventors:
|
Maignan; Jean (Tremblay les Conesse, FR);
Lang; Gerard (Saint Gratien, FR);
Malle; Gerard (Villiers sur Morin, FR)
|
| Assignee:
|
Societe Anonyme dite: L'Oreal (Paris, FR)
|
| Appl. No.:
|
528757 |
| Filed:
|
May 25, 1990 |
Foreign Application Priority Data
| Current U.S. Class: |
564/154; 564/152 |
| Intern'l Class: |
C07C 235/06 |
| Field of Search: |
564/154
|
References Cited
U.S. Patent Documents
| 2470945 | May., 1949 | Paul | 564/154.
|
| 2520293 | Aug., 1950 | Weiss | 564/154.
|
| 3300508 | Jan., 1967 | Shimizu et al. | 564/154.
|
| 3927091 | Dec., 1975 | Huber-Emden et al. | 564/154.
|
| 4009208 | Feb., 1977 | Lesher | 564/154.
|
Primary Examiner: Hollrah; Glennon H.
Assistant Examiner: Treanor; Susan P.
Attorney, Agent or Firm: Cushman, Darby & Cushman
Parent Case Text
This is a division of application No. 07/388,050, filed Aug. 2, 1989, now
U.S. Pat. No. 4,956,175.
Claims
What is claimed is:
1. A compound having the formula
##STR6##
wherein n is 2 or 3, and
m is 2 to 5 inclusive.
2. The compound of claim 1 selected from the group consisting of
bis (N-4-ethylhydroxy butyramide) disulfide,
bis (N-5-ethylhydroxy valeramide) disulfide,
bis (N-6-ethylhydroxy caproamide) disulfide,
bis (N-3-ethylhydroxy propionamide) disulfide,
bis (N-4-propylhydroxy butyramide) disulfide, and
bis (N-6-propylhydroxy caproamide) disulfide.
Description
The present invention relates to new
N-(mercaptoalkyl).OMEGA.-hydroxyalkylamides and their use, as reducing
agents, in the permanent deformation of hair.
The technique of effecting a permanent deformation of hair comprises, in a
first stage, the opening of the disulfide bonds of keratin (cystine) using
a composition containing a reducing agent (reducing stage), then
preferably after having rinsed the hair, reconstituting, in a second
stage, the said disulfide bonds by applying to the hair, under tension, an
oxidizing composition (oxidation stage, also called a fixation stage), so
as to give the desired form to the hair. This technique permits
indifferently, to effect either waving the hair, or uncurling or
uncrisping the hair.
Compositions to effect the first stage of a permanent waving operating are
generally provided in the form of lotions, creams, gels or powders to be
diluted in a liquid support and contain, preferably, a mercaptan as the
reducing agent.
Among these latter, those currently employed are thioglycolic acid and
thiolactic acid or a mixture of these acids, as well as their esters, for
example, the monothioglycolate of glycerol or glycol.
These reducing agents which are particularly effective in reducing the
disulfide bonds of keratin include, principally, thioglycolic acid which
can be considered as the product of choice in permanent waving operations.
It provides a reduction in the amount of about 50%.
These reducing agents exhibit, however, a major disadvantage since they
emit bad odors, characteristic of sulfur compounds, which at times render
the permanent waving operation distressing, not only for persons who
undergo such an operation, but also for persons effecting such an
operation.
With a view to reducing this disadvantage, a perfume is generally employed
to mask the odors.
Moreover, studies have been conducted with a view to perfecting new
odorless reducing agents. Thus, in Japanese patent application (Kokai) No.
260.058/86, the use of N-mercaptoalkylgluconamides, which are
water-soluble compounds, having weak volatility and practically odor free,
have been proposed.
These N-mercaptoalkylgluconamides are obtained by reaction of
glucono-.delta.-lactone with an aminoalkanethiol.
These new reducing agents, if they provide a remedy for the disadvantages
of known reducing agents, they do not possess however the excellent
reducing properties enjoyed principally by thioglycolic acid.
It has now been noted, in a quite surprising fashion, that by employing a
new class of mercaptoalkylamides, principally
N-(mercaptoalkyl).OMEGA.-hydroxyalkylamides, it is possible to remedy the
disadvantages of these various reducing agents.
The N-(mercaptoalkyl).OMEGA.-hyiroxyalkylamides, according to the present
invention, exhibit excellent reducing properties which are quite
comparable to those of thioglycolic acid but importantly they are odor
fee.
The present invention relates to, as a new industrial product, water
soluble N-(mercaptoalkyl).OMEGA.-hydroxyalkylamides, having the formula
##STR2##
wherein: n is 2 or 3, and
m is 2 to 5 inclusive.
In accordance with a preferred embodiment of the present invention, n is 2
and m is 3 or 4.
Representative N-(mercaptoalkyl).OMEGA.-hydroxyalkylamides of formula (I)
above, include principally the following:
4-hydroxy N-(2-mercaptoalkyl) butyramide,
3-hydroxy N-(2-mercaptoethyl) propionamide,
5-hydroxy N-(2-mercaptoethyl) valeramide,
4-hydroxy N-(3-mercaptopropyl) butyramide,
6-hydroxy N-(2-mercaptoethyl) caproamide and
6-hydroxy N-(3-mercaptopropyl) caproamide.
Among these, 4-hydroxy N-(2-mercaptoethyl) butyramide is particularly
preferred.
The present invention also relates to a process for preparing the
mercaptoalkylamides in accordance with the invention, this process
comprising reacting a mercaptoalkylamine (1) with a lactone (2) in
accordance with the following reaction scheme:
##STR3##
The mercaptoalkylamines (1) employed are either 2-mercaptoethylamine or
cysteamine (n=2) or 3-mercaptopropylamine (n=3).
The lactones (2) are .beta.-propionolactone (m=2), .gamma.-butyrolactone
(m=3), valerolactone (m=4) or caprolactone (m=5).
The reaction of opening the lactone is generally carried out under an inert
atmosphere in an alcohol such as methanol, ethanol, isopropanol or
butanol, and depending on the boiling point of the latter, at a
temperature between 20.degree. and 110.degree. C.
The reaction time is generally long and can require several days so that it
can be advantageous not to employ a solvent and to mix the
mercaptoalkylamine and the lactone in stoichiometric proportions and to
bring the mixture to a temperature between 20.degree. and 80.degree. C.
The evolution of the reaction is followed by dosage of the non-transformed
mercaptoalkylamine. When the reaction time is too long, an excess of
mercaptoalkylamine can advantageously be employed and the excess is
removed at the end of the reaction by filtering the mixture on a sulfonic
acid resin.
If, during the course of the reaction, a certain amount of thiol is
oxidized to the corresponding disulfide, the reaction mixture is then
diluted by twice its volume with water and stirred in the presence of a
mixture of sulfonic resin and zinc powder for 3 to 10 hours.
The majority of the disulfide being reduced, the mixture is then filtered,
thus resulting in a solution of the expected compound which can be used
directly.
In accordance with a preferred embodiment of the process of the present
invention, the percaptoalkylamines can be employed in the hydrochloride
form considered as the primary material, the free amine being liberated by
the triethanolamine. In this case, after the end of the reaction the
expected compound is obtained with an equivalent of triethanolamine
hydrochloride whose presence does not modify the properties of the
N-(mercaptoalkyl).OMEGA.-hydroxyalkylamides of the present invention.
It can be advantageous to operate in an autoclave which eliminates
sublimation problems of the cysteamine.
The present invention also relates to, as a new industrial product, the
disulfides of the compounds of formula (I) which can be represented by the
formula
##STR4##
wherein n and m have the same meanings as those given above for formula
(I).
The disulfides are usefully employed in compositions called
"self-neutralizers", i.e., they are combined with a thiol, such as for
example an N-(mercaptoalkyl).OMEGA.-hydroxyalkylamide of formula (I)
above, in molar amounts ranging from 0.5 to 2.5 and preferably from 1 to 2
(see U.S. Pat. No. 3,768,490).
The disulfides of formula (II) in accordance with the present invention are
obtained by oxidizing the compounds of formula (I) either in air or by
using, for example, H.sub.2 O.sub.2 in the optional presence of ferrous
ions.
They can also be obtained by reacting a disulfide of formula (3) with a
lactone (2) in accordance with the following reaction scheme:
##STR5##
Representative disulfides of formula (II) above include, principally, the
following:
bis (N-4-ethylhydroxy butyramide) disulfide,
bis (N-5-ethylhydroxy valeramide) disulfide,
bis (N-6-ethylhydroxy caproamide) disulfide,
bis (N-3-hydroxyethyl propionamide) disulfide,
bis (N-4-hydroxypropyl butyramide) disulfide and
bis (N-6-hydroxypropyl caproamide) disulfide.
The present invention also relates to a reducing composition, for the first
stage of a permanent deformation operation of hair comprising, in a
cosmetically acceptable vehicle, at least one
N-(mercaptoalkyl).OMEGA.-hydroxyalkylamide of formula (I) such as defined
above, as the reducing agent.
Preferably, the reducing agent is present in the composition according to
the invention in an amount between 2 and 20 weight percent and,
preferably, between 5 and 10 weight percent relative to the total weight
of the reducing composition.
The pH of the composition is generally between 6.5 and 10 and is obtained
using an alkaline agent such as, for example, ammonia, monoethanolamine,
diethanolamine, triethanolamine, an alkaline or ammonium carbonate or
bicarbonate.
The reducing composition can also contain various ingredients such as, for
example, cationic polymers such as those employed in the compositions of
French Patents Nos. 79.32078 and 80.2642 or even cationic polymers of the
ionene type, such as those used in the compositions of French Patent No.
82.17364, softening agents and principally quaternary ammonium derivatives
of lanolin, protein hydrolyzates, waxes, opacifying agents, perfumes,
dyes, non-ionic or cationic surface active agents, treating agents or even
penetration agents such as urea, pyrrolidone or thiomorpholinone.
The reducing composition according to the invention can also be of the
exothermic type, i.e., provoking a certain amount of heat during
application to the hair, which is agreeable to the person undergoing the
first stage of the permanent or uncurling of the hair.
The vehicle of the compositions according to the invention is preferably
water or a hydroalcoholic solution of a lower alcohol such as ethanol,
isopropanol or butanol.
When the compositions are intended for a hair uncurling or uncrisping
operation, the reducing composition is preferably in the form of a cream
so as to maintain the hair as rigid or stiff as possible. These creams are
provided in the form of "heavy" emulsions, for example, those based on
glyceryl stearate, glycol stearate, self-emulsifying waxes, fatty
alcohols, etc. Liquids or gels containing thickening agents, such as
carboxyvinyl polymers or copolymers which "glue" the hair can also be
employed so as to maintain the hair in a smooth position during the
setting period.
The present invention also relates to a hair waving process comprising
applying a reducing composition, such as defined above, to wet hair
previously rolled on rollers which have a diameter of 4 to 20 mm. The
composition can optionally be applied gradually on rolling the hair.
The reducing composition is then permitted to act on the hair for a period
of time ranging from 5 to 60 minutes and preferably 5 to 30 minutes. The
hair is then thoroughly rinsed after which there is applied to the rolled
up hair, an oxidizing composition so as to reform the disulfide bonds of
the keratin during a setting period of 2 to 10 minutes. After having
removed the rollers the hair is thoroughly rinsed.
The oxidation composition, or oxidizing agent, is of the type currently
employed and contains as the oxidizing agent H.sub.2 O.sub.2, an alkaline
bromate, a per salt or a mixture of an alkaline bromate and a per salt.
The concentration of H.sub.2 O.sub.2 can vary from 3 to 10 volumes; the
concentration of alkaline bromate, from 2 to 12 weight percent and that of
the per salt from 0.1 to 15 weight percent based on the total weight of
the oxidation composition.
The present invention also relates to a process for uncurling or uncrisping
the hair which comprises applying to the hair a reducing composition,
according to the invention, submitting the hair to a mechanical
deformation so as to fix the hair in a new form, by smoothing the hair
with a comb having large teeth or with the back of the comb or with the
hand. After a setting period of 5 to 60 minutes, particularly 5 to 30
minutes, the hair is again smoothed and then carefully rinsed. The
oxidation or fixing composition is then applied to the hair and left in
contact therewith for about 2 to 10 minutes. The hair is then thoroughly
rinsed.
There are now given, as an illustration and without any limiting character,
several examples of preparing the
N-(mercaptoalkyl).OMEGA.-hydroxyalkylamides and their disulfides, as well
as several examples of compositions containing them.
EXAMPLE I- Preparation of 4-hydroxy N-(2-mercaptoethyl) butyramide
(a) Reaction carried out at 80.degree. C. starting with cysteamine.
In a reactor, a mixture of 15.2 g of cysteamine and 15 cm.sup.3 of
.gamma.-butyrolactone is stirred under an inert atmosphere for 5 hours at
a temperature of about 80.degree. C. The disappearance of the
.gamma.-butyrolactone is followed by vapor phase chromatography (VPC).
When the .gamma.-butyrolactone is no longer detected in the reaction
mixture, the latter is poured into 100 cm.sup.3 of water to which are
added 10 g of sulfonic resin, "Dowex 50" (partially hydrated at 45%) and 5
g of zinc powder so as to reduce the small amount of disulfide being
formed during the course of the reaction. The whole is stirred for two
hours at ambient temperature and then filtered under an inert atmosphere.
A perfectly colorless aqueous solution is obtained. It is evaporated under
reduced pressure and 25 g of 4-hydroxy N-(2-mercaptoethyl) butyramide are
obtained.
It is a colorless liquid at ambient temperature.
The NMR'H 80 MHz conforms to the expected structure.
The thiol dosage in an acid medium is 95% and the elemental analysis
corresponds to a partially hydrated product: C.sub.6 H.sub.13 NO.sub.2
S.multidot.1/2H.sub.2 O
______________________________________
C H N O S
______________________________________
Calculated
41.84 8.19 8.13 23.22
18.62
Found 41.59 7.83 8.56 22.84
18.85
______________________________________
(b) Reaction carried out at ambient temperature starting with cysteamine
In a round bottom flask, 7.72 g of cysteamine and 8.61 g of
.gamma.-butyrolactone under an inert atmosphere are mixed. The mixture
thus obtained is stirred for 10 days at ambient temperature. The initially
pasty medium progressively becomes homogeneous so as to give a clear and
relatively mobile liquid. The total transformation of the
.gamma.-butyrolactone is verified at this stage by VPC and that of the
cysteamine by dosage with perchloric acid. The dosage of the thiol is
100%.
15 g of 4-hydroxy N-(2-mercaptoethyl) butyramide are obtained.
(c) Reaction carried out starting with cysteamine hydrochloride
In a reactor there are introduced, at ambient temperature and under an
inert atmosphere, 11.4 g of cysteamine hydrochloride and then slowly, with
stirring, 13.5 cm.sup.3 of triethanolamine. To the resulting mixture,
brought to a temperature of about 60.degree. C., 7.7 cm.sup.3 of
.gamma.-butyrolactone are slowly added. At the end of the introduction the
whole is brought to a temperature of 90.degree. C. for three hours, at the
end of which time all the .gamma.-butyrolactone is transformed (VPC
verification). 32 g of 4-hydroxy N-(2-mercaptoethyl) butyramide are
obtained containing one equivalent of triethanolamine hydrochloride in the
form of a pasty white solid that is conditioned under an inert atmosphere.
The dosages correspond to the expected mixture.
(d) Reaction carried out starting with cysteamine hydrochloride with
removal of the triethanolamine hydrochloride formed
Into a reactor, fitted with a mechanical stirrer, 228 g of cysteamine
hydrochloride are introduced and are placed under an argon atmosphere. 270
cm.sup.3 of triethanolamine are slowly added, with stirring, over a period
of about 1 hour 30 minutes. The pasty reaction mixture is then brought to
60.degree. C. and, at this temperature, 155 cm.sup.3 of
.gamma.-butyrolactone are slowly introduced. At the end of the addition,
the whole is then brought for 8 hours at 80.degree. C., at the end of
which time all the .gamma.-butyrolactone is transformed. 305 cm.sup.3 of
absolute ethanol are then introduced and stirring is maintained at
60.degree. C. for one-half hour.
The mixture is then cooled to about 15.degree. C. and the triethanolamine
hydrochloride is filtered. The filtrate is concentrated under reduced
pressure to remove the ethanol.
250 g of 4-hydroxy N-(2-mercaptoethyl) butyramide are obtained.
EXAMPLE II - Preparation of 5-hydroxy N-(2-mercaptoethyl) valeramide
A mixture, stirred under an inert atmosphere, of 5 g of cysteamine and 6.05
cm.sup.3 of .delta.-valerolactone is brought to a temperature of about
60.degree.-70.degree. C. for 15 hours. The disappearance of the
.delta.-valerolactone is followed by VPC. The reaction mixture is then
poured into 100 cm.sup.3 of water and 10 g of acid resin, "Dowex 50" and 3
g of zinc powder are added. The resulting mixture is stirred for 4 hours
at ambient temperature and then left overnight. The next day the mixture
is filtered and the water is evaporated under reduced pressure.
There are thus obtained 8 g of 5-hydroxy N-(2-mercaptoethyl) valeramide in
the form of a colorless liquid whose NMR'H spectrum, as well as the thiol
dosages and residual amine, conform to the expected structure.
EXAMPLE III - Preparation of 6-hydroxy N-(2-mercaptoethyl) caproamide
A mixture, under an inert atmosphere, of 5 g of cysteamine and 7.2 cm.sup.3
of .epsilon.-caprolactone is stirred for 6 hours at ambient temperature.
It is then left to stand overnight, after which the mixture is heated for
4 hours at a temperature of about 60.degree. C. At the end of this time
all the .epsilon.-caprolactone is transformed. The mixture is then poured
into 100 cm.sup.3 of water to which 10 g of acid resin, "Dowex 50" are
added and then 3 g of powdered zinc. The whole is stirred for 4 hours at
ambient temperature. The water is then removed under reduced pressure and
there are obtained 10 g of 6-hydroxy N-(2-mercaptoethyl) caproamide in the
form of a viscous liquid at ambient temperature whose NMR'H spectrum and
thiol dosages and residual amine correspond to the expected structure.
EXAMPLE IV - Preparation of bis (N-4-ethylhydroxy butyramide) disulfide
First Method
A solution of 20 g of 4-hydroxy N-(2-mercaptoethyl) butyramide in 300
cm.sup.3 of anhydrous ethanol is stirred in air in the presence of 20
cm.sup.3 of triethylamine for 48 hours at the end of which time the thiol
is transformed into the corresponding disulfide. The solvent and the
triethylamine are removed by evaporation under a vacuum.
The resulting pasty product is finely divided by stirring in methylene
chloride, filtered and then recrystallized in 200 cm.sup.3 of
acetonitrile.
15 g of bis (N-4-ethylhydroxy butyramide) disulfide in the form of white
crystals whose melting point is 102.degree. C. are obtained.
______________________________________
Elemental analysis: C.sub.12 H.sub.24 N.sub.2 O.sub.4 S.sub.2
C H N O S
______________________________________
Calculated
44.42 7.47 8.64 19.72
19.76
Found 44.55 7.51 8.47 20.02
19.67
______________________________________
Second Method
Into a reactor there are introduced, successively and at ambient
temperature, 11.26 g (0.05 mole) of cysteamine hydrochloride, 14.92 g (0.1
mole) of triethanolamine, 8.61 g (0.1 mole) of .gamma.-butyrolactone and
finally 20 cm.sup.3 of absolute ethanol. The resulting mixture is brought
for 4 hours to 80.degree. C.
The reaction mixture is then filtered on fritted glass. The solid and the
filtrate are separately treated.
The solid is taken up in 75 cm.sup.3 of boiling acetonitrile. The
insolubles are removed by filtration and the filtrate provides, on
cooling, 8.3 g of a white solid.
The filtrate is evaporated to dryness and then taken up with 30 cm.sup.' of
boiling acetonitrile. The insolubles are removed on fritted glass and the
filtrate gives, on cooling, 2.4 g of a white solid.
A total of 10.7 g of bis (N-4-ethylhydroxy butyramide) disulfide having a
melting point of 98.degree.-100.degree. C. are obtained.
The NMR'H 80 MHz spectrum conforms to the expected structure.
In accordance with the same operating procedures described above the other
disulfides mentioned above have been obtained.
EXAMPLE V - Preparation of bis (N-5-ethylhydroxy valeramide) disulfide
To a solution of 1.77 g (0.1 mole) of 5-hydroxy N-(2-mercaptoethyl)
valeramide in 20 cm.sup.3 of absolute alcohol, cooled to +5.degree. C.,
4.6 cm.sup.3 (0.045 mole) of 30% H.sub.2 O.sub.2 are slowly added.
Stirring is then maintained for 1 hour while letting the temperature return
to ambient temperature. The thiol dosage is negative. The reaction medium
is then evaporated to dryness under reduced pressure. After prolonged
drying under a vacuum at ambient temperature, 1.5 g of bis
(N-5-ethylhydroxy valeramide) disulfide are obtained which slowly
crystallizes under the form of a white waxy solid.
The NMR'H 80 MHz spectrum conforms to the expected structure.
EXAMPLE VI - Preparation of bis (N-6-ethylhydroxy caproamide) disulfide
To a solution of 1.92 g (0.1 mole) of 6-hydroxy N-(2-mercaptoethyl)
caproamide in 20 cm.sup.3 of ethanol, cooled to +5.degree. C., 5.0
cm.sup.3 (0.049 mole) of 30% H.sub.2 O.sub.2 are slowly added with
stirring. After 2 hours of stirring at ambient temperature (thiol test
negative) the solution is clarified by paper filtration and then
evaporated to dryness under reduced pressure. After prolonged drying under
a vacuum at ambient temperature 1.7 g of bis (N-6- ethylhydroxy
caproamide) disulfide in the form of a thick pale yellow gel are obtained.
The NMR' 80 MHz spectrum conforms to the expected structure.
Composition Examples
I - In accordance with the invention, a permanent deformation reducing
composition for hair is prepared by admixing the following ingredients:
______________________________________
4-hydroxy N-(2-mercaptoethyl butyramide
9 g
Ammonia, sufficient amount for pH = 9
Perfume 0.1 g
Preservative 0.5 g
Demineralized water, sufficient amount for
100 g
______________________________________
This composition is applied to moistened hair, previously rolled on hair
setting rollers. After permitting the composition to act for about 15
minutes the hair is thoroughly rinsed with water. The following oxidation
composition is then applied to the hair:
______________________________________
H.sub.2 O.sub.2, sufficient amount for
8 volumes
Stabilizer 0.3 g
Perfume 0.1 g
Lactic acid, sufficient amount for pH = 3
Demineralized water, sufficient amount for
100 g
______________________________________
The oxidizing composition is permitted to act on the hair for about 10
minutes. The rollers are removed and the hair is thoroughly rinsed with
water.
After drying under a hood the hair exhibits beautiful curls.
In this example the reducing composition can advantageously be replaced by
one of the following reducing compositions:
______________________________________
(A)
4-hydroxy N-(2-mercaptoethyl butyramide)
12 g
Monoethanolamine, sufficient amount for pH = 9
Perfume 0.1 g
Preservative 0.5 g
Demineralized water, sufficient amount for
100 g
(B)
5-hydroxy N-(2-mercaptoethyl) valeramide
10 g
Monoethanolamine, sufficient amount for pH = 8.5
Perfume 0.1 g
Preservative 0.5 g
Demineralized water, sufficient amount for
100 g
(C)
6-hydroxy N-(2-mercaptoethyl) caproamide
7 g
Ammonia, sufficient amount for pH = 8.5
Perfume 0.1 g
Preservative 0.5 g
Demineralized water, sufficient amount for
100 g
______________________________________
II - In accordance with the invention, a composition is prepared to effect
a "self-neutralizing" permanent by admixing the following components:
______________________________________
4-hydroxy N-(2-mercaptoethyl) butyramide
6.3 g
Bis (N-4-ethylhydroxy butyramide)
17.5 g
disulfide
Urea 8 g
Perfume 0.1 g
Preservative 0.5 g
Ammonia, sufficient amount for pH = 9.5
Water, sufficient amount for
100 g
______________________________________
This solution is applied to moistened hair, previously rolled up on hair
setting rollers and is permitted to remain in contact with the hair for
about 20 minutes. The rollers are removed and the hair is thoroughly
rinsed with water.
After drying under a hood the hair exhibits beautiful waves.
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